CN101880396B - Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation - Google Patents
Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation Download PDFInfo
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Abstract
The invention relates to a preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation, which aims at solving the technical problems that the surface tension of LED encapsulating silicon rubber is reduced, so the LED encapsulating silicon rubber is convenient for the vacuum defoamation, and the transmittance of the product is improved. The method comprises the following steps that: 1) transparent vinyl silicon oil containing methyl trifluoropropyl silica chain link and methyl-phenyl silica chain link is prepared; 2) transparent vinyl silicon oil is configured with methyl-phenyl hydrogen-containing silicon oil, platinum catalyst and inhibitor to A/B rubber; the mol ratio of Si-H and Si-Vi is 0.8 to 3: 1; the hydrogen content of the methyl-phenyl hydrogen-containing silicon oil is 1.6 to 1.0*10<-6> percent by weight; 3) A/B rubber is uniformly mixed, after being vacuum defoamed at the room temperature, the mixture is vulcanized to a product.
Description
Technology
The present invention relates to an unreported, trifluoropropyl methyl silicone-containing chain and methyl phenyl silicone chain, easy to vacuum deaeration of the LED package with the preparation of silicone rubbers. Silicone rubber of the present invention has excellent properties such as high refractive index, high transmittance, radiation-resistant, high temperature resistance, weatherability, can be used as LED packaging materials, is also expected to be used for other sealants, potting materials and adhesives .
BACKGROUND
Ultra-high brightness light-emitting diode (LED) consumption of electricity of a traditional light sources, 1/10, with no serious pollution of the environment with mercury, small size, long life and other characteristics, first into industrial equipment, instrumentation, traffic lights, car , backlight and other special lighting. With high brightness LED performance improvements, power LED is expected to replace incandescent, fluorescent and other traditional sources to become the fourth generation of lighting.
LED packaging material needs to have excellent luminous efficiency, high refractive index (n D 25 > 1.50) and high transmittance (i.e. in the visible light (400 ~ 800 nm) range, the light transmittance greater than 98%, 10 mm). Bisphenol A type epoxy resin used as a normal transparent LED packaging materials for nearly 30 years of history, but the face of which the power LED high temperature, high UV intensity and other complex environmental conditions, easy to yellowing epoxy exposed , rattle and other performance deficiencies, unable to adapt to the development needs of power LED.
Organic silicon material is an ideal LED packaging materials, domestic lighting related enterprises and research institutions have invested a lot of manpower and resources, the LED encapsulation silicone materials conduct extensive research. Add molding liquid silicone rubber can be used for LED packaging materials. JP ,2006-324596 reported in Canadian molding liquid silicone rubber injection molding at 165 ℃ under obtain shrinkage rate of 3.37%, contraction ratio is only 0.04, refractive index 1.50 to 1.60 of the packaging materials. US2007-7291691 and even get up to 50 Shore D hardness, elastic modulus of 350 ~ 1500 MPa, 88% light transmittance of 92% (wavelength 400 nm, sample thickness 4mm) of the LED package material. Forming liquid silicone rubber to the processing amount of the inorganic filler is added (such as boron, silicon, titanium, aluminum, zinc oxide, etc.) can improve the material properties of heat resistance and resistance to radiation, the LED package material obtained using 450 ~ 140 ℃ 470 nm wavelength light irradiation 1000 h, down less than 10% transmittance. Generally, LED packaging materials require curing at a temperature 2 ~ 5 h, longer production cycle. US2008-7314770 with D
4And 1,3 - divinyl-1 ,1,3,3, - tetramethyl disiloxane (vinyl double head) in concentrated sulfuric acid-catalyzed ring-opening polymerization to obtain vinyl silicone oil; then, to add hydrogen silicone oil, platinum catalyst and sensitizer, after mixing with visible light or ultraviolet light 2.5 ~ 20 min can be cured completely, get better performance of the LED packaging materials.
Vinyl silicone resin and silicone oil through hydrosilylation vulcanization molding, can be prepared silicone LED packaging materials. To obtain a high refractive index, radiation-resistant packaging materials, silicone, vinyl silicone and silicone oil is generally required to contain a certain amount of chain diphenyl silicone or methylphenyl silicone chain. US2004-0116640 and US2007 -7294682 reported with chlorosilane were obtained by hydrolysis and condensation processes vinyl silicone resin, and then the oxygen-containing phenyl silicone chain of silicone oil in the platinum catalyst under vulcanization molding, access LED packaging materials。The refractive index of the material of up to 1.51 Shore hardness D 75 ~ 85 degrees, the bending strength of 95 ~ 135 MPa, tensile strength 5.4 MPa, 500 h after UV radiation transmission rate reduced to 92% of 95%. Such silicone materials to reduce shrinkage, improve its resistance to thermal shock cycling performance, can improve the sealing material mass fraction of phenyl, to obtain low shrinkage, resistance to radiation, heat, light transmission rate of 95% packaging materials; even obtained having excellent mechanical properties and adhesion properties, can withstand 1000 -50 ℃ / 150 ℃ thermocycling impact without cracking silicone encapsulating material. Because without reinforcement, these organic silicon poor mechanical strength of packaging materials, packaging materials can not meet some of LED technology requirements. JP 2005-0212008A1 and EP ,2004-1424363A1 of methyl phenyl silicone oil and a vinyl silicone resin of fumed silica was added, heat conductive filler, light adjusting agents, flame retardants, etc., in 120 ~ 180 ℃ curing 30 ~ 180 min after the bending strength of packaging material 95 ~ 100 MPa, a tensile strength of 5.4 MPa, Shore hardness D 75 ~ 85 degrees, the refractive index as high as 1.51; by 400 nm radiation for 100 h light transmittance from 95% down to 92%, and 500 h after irradiation is still 92%.
With vinyl silicone resins and vinyl silicone oil and silicone oil blends via hydrosilylation curing process, can play a silicone resins and silicone rubber respective advantages of high performance LED packaging materials. US2007-7282270 obtained by this method of the LED package material the refractive index of 1.54, the transmittance of 85 to 100%, Shore A hardness of 45 to 95 degrees, the tensile strength of 1.8 MPa, at 100 h 150 ℃ heating surface to appear cracks.
In recent years, studies have begun domestic active, Institute of Chemistry Michael etc. (CN1978526 and CN101085855) prepared a UV-resistant and high-temperature aging silicone epoxy resin composition by blending, casting, curing, obtained has excellent optical transparency and excellent UV resistance, high temperature aging properties, can be used to power LED packaging materials. Fudan University and other amusement spread TANG (CN101525466 and CN101525467) reported with an epoxy resin, a silicone resin, such as acidic inorganic nanoparticles through a simple physical mixing, in acidic catalysis inorganic nanoparticles vulcanization molding, an epoxy / organic Silicon / inorganic hybrid material, can be used as LED packaging materials. However, these packaging materials containing epoxy groups, there are still easy to yellowing and other defects.
...
In recent years, studies have begun domestic active, Institute of Chemistry Michael etc. (CN1978526 and CN101085855) prepared a UV-resistant and high-temperature aging silicone epoxy resin composition by blending, casting, curing, obtained has excellent optical transparency and excellent UV resistance, high temperature aging properties, can be used to power LED packaging materials. Fudan University and other amusement spread TANG (CN101525466 and CN101525467) reported with an epoxy resin, a silicone resin, such as acidic inorganic nanoparticles through a simple physical mixing, in acidic catalysis inorganic nanoparticles vulcanization molding, an epoxy / organic Silicon / inorganic hybrid material, can be used as LED packaging materials. However, these packaging materials containing epoxy groups, there are still easy to yellowing and other defects.
...
New Materials Co., Ltd., Dongguan City, Betley Su Jun Liu, etc. (CN101016446) with a vinyl-terminated poly methyl phenyl siloxane, vinyl methyl silicone resin, poly phenyl methyl hydrogen siloxane, catalysts and inhibition agent is prepared by mixing silicone LED packaging materials, light transmission rate of up to 99%, refractive index up 1.49 to 1.53, well suited for LED and other electronic products packaging. Shanghai University, Li Qinghua, etc. (CN101381516) invented a LED using RTV silicone sealant, is capped by a poly-vinyl-phenyl siloxane, vinyl dimethyl-silyloxy-capped poly methyl siloxane, phenyl methyl hydrogen siloxane and inhibitor methylbutynol obtained by hydrosilylation, has good heat resistance, moisture resistance, light transmittance of 99%, the refractive index up to 1.47 to 1.55. But these two patents are the main chain diphenyl siloxane chain, and its resistance to ultraviolet radiation performance needs to be improved.
...
New Materials Co., Ltd., Dongguan City, Betley Su Jun Liu, etc. (CN101016446) with a vinyl-terminated poly methyl phenyl siloxane, vinyl methyl silicone resin, poly phenyl methyl hydrogen siloxane, catalysts and inhibition agent is prepared by mixing silicone LED packaging materials, light transmission rate of up to 99%, refractive index up 1.49 to 1.53, well suited for LED and other electronic products packaging. Shanghai University, Li Qinghua, etc. (CN101381516) invented a LED using RTV silicone sealant, is capped by a poly-vinyl-phenyl siloxane, vinyl dimethyl-silyloxy-capped poly methyl siloxane, phenyl methyl hydrogen siloxane and inhibitor methylbutynol obtained by hydrosilylation, has good heat resistance, moisture resistance, light transmittance of 99%, the refractive index up to 1.47 to 1.55. But these two patents are the main chain diphenyl siloxane chain, and its resistance to ultraviolet radiation performance needs to be improved.
...
To facilitate vacuum deaeration, low surface tension can be added to the material, but because of the refractive index of these materials of the LED package material refractive index differences, will affect the transmittance of packaging materials, packaging materials or not transparent. Better approach is to packaging materials in the molecular chain to introduce some groups to reduce the surface tension of packaging materials, such materials can ensure transparency, but also easy to vacuum degassing. Typically, the fluorine-containing polysiloxane low surface tension. Accordingly, the LED package of the present invention in the preparation of a vinyl silicone base polymer process, the dimethyl siloxane ring (D
...n To facilitate vacuum deaeration, low surface tension can be added to the material, but because of the refractive index of these materials of the LED package material refractive index differences, will affect the transmittance of packaging materials, packaging materials or not transparent. Better approach is to packaging materials in the molecular chain to introduce some groups to reduce the surface tension of packaging materials, such materials can ensure transparency, but also easy to vacuum degassing. Typically, the fluorine-containing polysiloxane low surface tension. Accordingly, the LED package of the present invention in the preparation of a vinyl silicone base polymer process, the dimethyl siloxane ring (D
...n Me，Vi, N = 3,4,5, etc), methyl phenyl siloxane ring (Dn Me,Ph, N = 3,4,5, etc) added to the amount of raw materials such as trifluoropropyl methyl siloxane ring, in the catalyst of ring-opening polymerization, on the one hand to obtain a high refractive index, high transmittance ethylene based base polymer, on the other hand to the introduction of product molecules trifluoropropyl methyl silicone chain, reducing the surface tension of the product, to obtain easy vacuum deaeration of the LED package with an organic silicone rubber.
SUMMARY OF THE INVENTION
The present invention is to solve the technical problem is to reduce the LED package surface tension of silicone rubber, silicone rubber such that the LED package to facilitate vacuum deaeration, to reduce the defect rate during the LED package, and increase the light transmittance.
The present invention is easy to vacuum defoaming of the LED package with the preparation of silicone rubbers, characterized by the steps of:
A) Preparation of transparent vinyl silicone oil: the N2Under the protection of the water removal under reduced pressure was added to the polymerizable monomer capping agent in the catalyst of the ring-opening polymerization; polymerization reaction or after the decomposition by heating the catalyst was removed by filtration, and removal of low molecular weight high temperature under reduced pressure compounds, cooled to room temperature, ie trifluoropropyl methyl silicone-containing chain and methyl phenyl silicone chain transparent vinyl silicone oil;
The polymerization reaction following general formula:
Where Dn， D
n Me,Vi，D
n Me,Ph，D
n Me，FChemical structural formula is as follows:
，
The resulting clear vinyl silicone oil of formula ViMe2(MeViSiO)
m(MePhSiO)
p(Me
2SiO)
q (MeCH
2CH
2CF
3SiO)
kMe
2Vi, wherein, m, p, q and K is 0 or a positive integer, 0 ≤ m ≤ 580,0 ≤ p ≤ 3308,0 ≤ q ≤ 3289,0 ≤ k ≤ 384, and satisfy m / (m + p + q + k) = 0 ~ 0.1, p / (m + p + q + k) = 0.5 ~ 0.9, q / (m + p + q + k) = 0.1 ~ 0.5, k / (m + p + q + k) = 0 ~ 0.12; vinyl silicone oil molecular weight of 500 ~ 50 × 104 。A molecular weight of transparent vinyl silicone oil 500 ~ 50 × 104, The refractive index nD 251.50 to 1.54, it can be used with LED package silicone rubber base polymer.
2) in step 1) with a crosslinking agent obtained transparent vinyl silicone oil - methylphenyl silicone oil, and a platinum catalyst inhibitor formulated into A / B plastic; A transparent vinyl silicone rubber, a platinum catalyst and inhibition mixtures, according to the amount of platinum catalyst is a platinum atom silicone rubber mass, of the total mass of 2 ~ 50ppm, in accordance with the amount of inhibitors and inhibitors of the molar ratio of platinum atoms 1 ~ 100:1; B containing gel as methylphenyl hydrogen silicone oil, or a methyl phenyl silicone oil and a mixture of transparent vinyl silicone oil, methylphenyl silicone oil in which the amount of B are the weight of the gum 0.01 ~ 99.99%; A / B transparent vinyl silicone gum total dosage, when the A / B gel after mixing, to make one of the Si-H (Si - H) and the Si-Vi (Si - vinyl) molar ratio of 0.8 ~ 3:1 (preferably 1 to 1.5:1 ); said methylphenyl silicone oil containing hydrogen content of 1.6wt% ~ 1.0 × 10
...-6wt％；
2) in step 1) with a crosslinking agent obtained transparent vinyl silicone oil - methylphenyl silicone oil, and a platinum catalyst inhibitor formulated into A / B plastic; A transparent vinyl silicone rubber, a platinum catalyst and inhibition mixtures, according to the amount of platinum catalyst is a platinum atom silicone rubber mass, of the total mass of 2 ~ 50ppm, in accordance with the amount of inhibitors and inhibitors of the molar ratio of platinum atoms 1 ~ 100:1; B containing gel as methylphenyl hydrogen silicone oil, or a methyl phenyl silicone oil and a mixture of transparent vinyl silicone oil, methylphenyl silicone oil in which the amount of B are the weight of the gum 0.01 ~ 99.99%; A / B transparent vinyl silicone gum total dosage, when the A / B gel after mixing, to make one of the Si-H (Si - H) and the Si-Vi (Si - vinyl) molar ratio of 0.8 ~ 3:1 (preferably 1 to 1.5:1 ); said methylphenyl silicone oil containing hydrogen content of 1.6wt% ~ 1.0 × 10
...
Step 1), said polymerizable monomer consists of dimethyl siloxane ring, methyl vinyl siloxane ring, a phenyl ring methyl siloxane and trifluoropropyl methyl siloxane ring component; wherein the dimethyl siloxane ring of the total polymerizable monomer 10 ~ 50mol%, methyl vinyl siloxane ring of the total polymerizable monomer 0.002 ~ 10mol%, trifluoropropyl methyl siloxane ring the total amount of the polymerizable monomer alkoxy 0.05 ~ 12mol%; methyl phenyl siloxane ring of the total amount of the remaining polymerizable monomer molar hundred percent;
Dimethyl siloxane ring of the hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane in one or more siloxane, or a dimethyl silicone ring alumoxane mixture (DMC); the methyl vinyl siloxane ring trivinyl trimethyl cyclotrisiloxane, vinyl tetramethyl cyclotetrasiloxane, pentamethyl-five vinylcyclohexene pentasil oxygen in one or more alkyl; said methyl phenyl siloxane ring is three triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, pentamethyl pentaphenylbenzaldehyde cyclopenta siloxane in one or more, or a mixture of methyl phenyl ring body; the trifluoropropyl methyl-trifluoropropyl methyl siloxane ring cyclotrisiloxane methyltriethoxysilane fluoropropyl cyclotetrasiloxane, cyclopentasiloxane trifluoropropyl methyl siloxane in one or more of;
...
Dimethyl siloxane ring of the hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane in one or more siloxane, or a dimethyl silicone ring alumoxane mixture (DMC); the methyl vinyl siloxane ring trivinyl trimethyl cyclotrisiloxane, vinyl tetramethyl cyclotetrasiloxane, pentamethyl-five vinylcyclohexene pentasil oxygen in one or more alkyl; said methyl phenyl siloxane ring is three triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, pentamethyl pentaphenylbenzaldehyde cyclopenta siloxane in one or more, or a mixture of methyl phenyl ring body; the trifluoropropyl methyl-trifluoropropyl methyl siloxane ring cyclotrisiloxane methyltriethoxysilane fluoropropyl cyclotetrasiloxane, cyclopentasiloxane trifluoropropyl methyl siloxane in one or more of;
...
The catalyst of 98% concentrated sulfuric acid, CF3SO
3H, phosphate, acid clay, strongly acidic cation exchange resin, earth solid superacid, tetramethyl ammonium hydroxide, tetramethyl ammonium hydroxide silicon alkoxide, tetraethyl ammonium hydroxide, tetraethyl ammonium hydroxide silanol salt, tetrabutylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium hydroxide silicon alkoxide, hydroxide, tetrabutyl phosphonium hydroxide, tetrabutyl phosphine silicon alkoxide, KOH in one or more of;
The platinum catalyst is chloroplatinic acid, H2PtCl
6In isopropanol (i-PrOH) solution, H2PtCl
6In tetrahydrofuran (THF) solution, Pt (PPh3)
4、Cp
2PtCl
2, Methyl vinyl siloxane complex of the platinum complex, diethyl phthalate, platinum coordination complexes, platinum dichloride dicyclopentadiene, dichlorobis (triphenylphosphine) in in one platinum complex;
The inhibitor of quinoline, pyridine, t-butyl hydroperoxide, propargyl alcohol, tetramethylammonium Alkynols in one;
Step 1) The polymerization reaction temperature is 20 ~ 100 ℃, the polymerization reaction time is 1 ~ 20h; high temperature under reduced pressure to remove the low molecular weight compound in-0.096MPa for gradually heated to 205 ℃;
Step 3) at room temperature vacuum deaeration time is 1 ~ 60 min, the curing temperature is 20 ~ 150 ℃.
Advantageously, step 1) a polymerizable monomer is removed under reduced pressure water temperature 35 ~ 45 ℃ / pressure of 0.096Mpa; polymerization temperature is 80 ~ 100 ℃, the polymerization time is 1 ~ 5h; low molecular weight compounds removed under reduced pressure in-0.096MPa gradually under heating to 205 ℃; step 3) at room temperature vacuum deaeration time is 5 ~ 40min, the curing temperature is 80 ~ 120 ℃.
Advantageously, when the platinum catalyst is H2PtCl
6In isopropanol (i-PrOH) solution, H2PtCl
6In tetrahydrofuran (THF) solution of methyl vinyl siloxane complex in a platinum, the amount by mass of platinum atoms silicone rubber, of the total mass of 2 ~ 30ppm (most preferably 2 ~ 10ppm).
Lack of the prior art, the LED package vinyl silicone rubber base polymer during preparation, the product molecules by introducing a certain amount of methyl trifluoropropyl silicone chain, reducing the surface tension of the product, the LED package silicone material to facilitate vacuum deaeration, to solve the LED package of the product is difficult to vacuum deaeration, affecting product quality problem.
The method of the present invention is prepared by silicone rubber, is not reported, the trifluoropropyl methyl silicone-containing chain and methyl phenyl silicone chain methyl phenyl silicone rubber.
The background art, the present invention is to silicone-containing methylphenyl silicone chain vinyl trifluoropropyl group introduced into the molecular chain silicone, reduces the LED package with the surface tension of the silicone rubber, so that the LED package prepared materials to facilitate the vacuum degassing, improved transmittance of the LED package material, reducing the rate of defective LED device. In addition, the LED package resulting silicone rubber also has excellent performance, such as having a longer operating time, high refractive index, high transmittance, radiation-resistant, high temperature resistance, weatherability, is also expected to be used for other sealants , sealant and adhesives.
BRIEF DESCRIPTION
Figure 1 shows the different contents of trifluoropropyl methyl silicone chain of vulcanization molding properties of silicone rubber. The resulting silicone rubber is prepared in the present invention is trifluoropropyl methyl silicone-containing chain and methyl phenyl silicone chain vinyl methyl phenyl silicone oil as the base polymer, according to Si-H: Si-Vi = 1.2:1 mixed and compound 5ppm platinum catalysts and inhibitors in accordance with the molar ratio of platinum atoms 30:1 methylbutynol, preparation of a / B plastic, and have been audited 5min, 10min, 20min and 30min vacuum deaeration, after vacuum discharge bulbs and heating temperature curing derived. Among
Figure 1a without D3 Me,F ；
Figure 1b is added 1mol% D3 Me,F, A base polymer of methyl vinyl silicone Trifluoropropyl chain content 0.7mol%;
Figure 1c is added 3mol% D3 Me,F, A base polymer of methyl vinyl silicone Trifluoropropyl chain content 1.44mol%;
Figure 1d is added 5mol% D3 Me,F, A base polymer of methyl vinyl silicone Trifluoropropyl chain content 4.28mol%;
Figure 1e is added 7 mol% D3 Me,F, A base polymer of methyl vinyl silicone Trifluoropropyl chain content 5.3 mol%.
After curing the samples from the above electron micrograph (magnification 100x) shows that when trifluoropropyl methyl siloxane ring an amount of about 5-7mol%, the bubbles can be well removed.
After curing the samples from the above electron micrograph (magnification 100x) shows that when trifluoropropyl methyl siloxane ring an amount of about 5-7mol%, the bubbles can be well removed....
After curing the samples from the above electron micrograph (magnification 100x) shows that when trifluoropropyl methyl siloxane ring an amount of about 5-7mol%, the bubbles can be well removed....
The following examples, the technical solution of the present invention is further specifically described.
...
The following examples, the technical solution of the present invention is further specifically described.
...
Example 1
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, gel permeation chromatography (GPC, THF as the mobile phase and polystyrene as standard sample, the same below) measured a number average molecular weight of 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and the molar ratio of silicon atoms (Ph / Si, the same below) is 0.784. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more (sample thickness 10mm, the same below).
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi mixing molar ratio of 1.2:1, a platinum catalyst added to 5ppm, while according to the atomic molar ratio of inhibitor to platinum ratio of 30:1 Join methylbutynol, preparation of a / B plastic; B gel crosslinking methylphenyl silicone oil quality as the total mass of B glue 0.1wt%.
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1a).
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1a)....
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1a)....2Under the protection of the bottle to 250mL dry three monomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4（9.305g，0.0314mol）、D
3 Me,FUnder the protection of the bottle to 250mL dry three monomer D...2Under the protection of the bottle to 250mL dry three monomer D...D 25= 1.5315, GPC number average molecular weight measured 0.65 × 104, The molecular weight distribution width (MWD) was 1.64, the1H-NMR measured mass percent of Si-Vi 4.47 × 10-4mol / g, Ph / Si 0.784. Trifluoromethyl-propyl siloxane chain content 0.7mol%, as measured by surface tension meter surface tension 31.439 mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H: Si-Vi = 1.2:1 mixed and 5ppm platinum catalyst compound, and according to the atomic molar ratio of inhibitor to platinum 30:1 a alkynols, preparation of a / B glue, B gel crosslinking methylphenyl silicone oil quality as the total mass of B glue 0.1wt%.
3) the resulting A / B plastic by vacuum deaeration, the vulcanization at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1b).
Example 3
1) in N2Under the protection of the bottle to 250mL dry three monomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（1.075g，0.035mol）、D
4（7.842g，0.02649mol）、D
3 Me,F(3.4719g, 0.00741mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), 6.23g strongly acidic cation exchange resin, the N2Protection, 100 ℃ polymerized 5h, then filtered to remove the catalyst. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the product was a colorless transparent, the LED package is vinyl silicone rubber base polymer, Abbe refractometer measured obtaining the refractive index nD 25= 1.5305, GPC number average molecular weight measured 0.40 × 104, The molecular weight distribution width (MWD) was 1.64, the1H-NMR as measured Si-Vi content was 4.60 × 10-4mol / g, Ph / Si is 0.806, trifluoropropyl methyl silicone chain content 1.44 mol%, measured by a surface tension meter Surface tension 29.318 mN / m, as measured by UV spectrophotometer at 800nm Transmittance up to 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H: Si-Vi = 1.2:1 mixed and 5ppm platinum catalyst compound, and according to the atomic molar ratio of inhibitor to platinum 30:1 a alkynols, preparation of a / B glue, B gel crosslinking methylphenyl silicone oil quality as the total mass of B glue 0.1wt%.
3) the resulting A / B plastic by vacuum deaeration, the vulcanization at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1c).
Example 4
1) in N2Under the protection of the bottle to 250mL dry three monomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（1.075g，0.035mol）、D
4（6.379g，0.02155mol）、D
3 Me,F(5.7865g, 0.01235mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), 2.48g of tetraethyl ammonium hydroxide, silicon alkoxide, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the product was a colorless transparent, the LED package is vinyl silicone rubber base polymer, Abbe refractometer measured obtaining the refractive index nD 25= 1.5290, GPC number average molecular weight measured 0.61 × 104, The molecular weight distribution width (MWD) was 1.58, the1H-NMR measured mass percent of Si-Vi 3.6 × 10-4mol / g, Ph / Si is 0.798, trifluoropropyl methyl silicone chain content 4.28mol%, measured by a surface tension meter Surface tension 26.869 mN / m, as measured by UV spectrophotometer at 800nm Transmittance up to 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H: Si-Vi = 1.2:1 mixed and 5ppm platinum catalyst compound, and according to the atomic molar ratio of inhibitor to platinum 30:1 a alkynols, preparation of a / B glue, B gel crosslinking methylphenyl silicone oil quality as the total mass of B glue 0.1wt%.
3) the resulting A / B plastic by vacuum deaeration, the vulcanization at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1d).
Example 5
1) in N2Under the protection of the bottle to 250mL dry three monomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（1.075g，0.035mol）、D
4（4.917g，0.01661mol）、D
3 Me,F(8.1011g, 0.01729mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), 6.23g acid clay, the N2Protection, 100 ℃ polymerized 5h, then filtered to remove the catalyst. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5275, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 3.6 × 10-4mol / g, Ph / Si (molar ratio) was 0.797, trifluoropropyl methyl silicone chain content 5.3mol%, measured by a surface tension meter Surface tension 25.333 mN / m, measured at 800nm using UV spectrophotometer when the light transmission rate up to 96%.
2) the silicone oil and the obtained vinyl based polymer according to Si-H: Si-Vi = 1.2:1 mixed and 5ppm platinum catalyst compound, and according to the atomic molar ratio of inhibitor to platinum 30:1 a alkynols, preparation of a / B glue, B gel crosslinking methylphenyl silicone oil quality as the total mass of B glue 0.1wt%.
3) the resulting A / B plastic by vacuum deaeration, the vulcanization at 100 ℃ 2h, obtain an LED package with a silicone rubber (see Figure 1e).
Example 6
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi mixing molar ratio of 0.8:1, a platinum catalyst added to 15ppm, while according to the atomic molar ratio of inhibitor to platinum ratio of 50:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 0.08wt%.
3) the resulting A / B plastic were degassed under vacuum, cured at 120 ℃ 2h, obtain an LED package with silicone rubber.
Example 7
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi mixing molar ratio of 1.5:1, adding a platinum catalyst 8ppm, while according to the atomic molar ratio of inhibitor to platinum ratio of 20:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 30wt%.
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with silicone rubber.
Example 8
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi molar ratio of 2:1, adding a platinum catalyst 8ppm, while according to the atomic molar ratio of inhibitor to platinum ratio of 50:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 80wt%.
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with silicone rubber.
Example 9
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi mixing molar ratio of 3.5:1, adding a platinum catalyst 8ppm, while according to the atomic molar ratio of inhibitor to platinum ratio of 100:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 99.9wt%.
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with silicone rubber.
Example 10
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi mixing molar ratio of 1.2:1, while adding 8ppm platinum catalyst inhibitor in accordance with the molar ratio of platinum atoms in the proportion of 30:1 propargyl alcohol, preparation of a / B glue, B gel crosslinking methylphenyl silicone oil quality as the total mass of B glue 0.01wt%.
3) the resulting A / B plastic were degassed under vacuum, cured at 100 ℃ 2h, obtain an LED package with silicone rubber.
Example 11
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi molar ratio of 1.5:1 were mixed, 8ppm platinum catalyst, and follow the atomic molar ratio of inhibitor to platinum ratio of 30:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 15wt%.
3) the resulting A / B were treated plastic vacuum deaeration after curing at 150 ℃ 1h, obtain an LED package with silicone rubber.
Example 12
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi molar ratio of 1.5:1 were mixed, 8ppm platinum catalyst, and follow the atomic molar ratio of inhibitor to platinum ratio of 1:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 0.1wt%.
3) the resulting A / B plastic were degassed under vacuum, at 80 ℃ curing 3h, obtain an LED package with silicone rubber.
Example 13
1) in N2Under the protection of a dry three to 250mL flaskPolymerizationMonomer Dn Me,Ph（109.75 g，0.2022mol）、D
4 Me,Vi（4.3g，0.035mol）、D
4(10.035g, 0.0339mol). At 35 ℃ ~ 45 ℃ /-0.096MPa the removal of monomers in the water, and then capping agent added 1,1,3,3 - tetramethyl-1 ,3 - divinyl siloxane (0.93 g, 0.005mol), tetramethylammonium hydroxide catalyst, silicon alkoxide 2.48g, the N2Protection, 100 ℃ polymerized 5h, and then decomposed at 150 ℃ 3-4h until the exhaust catalyst is neutral. Under reduced pressure to-0.096MPa, gradually warming to remove low molecular weight compound 205 ℃, 5min fractions when there is no heating was stopped, cooled to room temperature, the resulting product is colorless and transparent silicone rubber vinyl LED package base polymer, A Tony refractometer measured obtaining the refractive index nD 25= 1.5350, GPC number average molecular weight measured 0.83 × 104, The molecular weight distribution width (MWD) of 1.81, the1H-NMR as measured Si-Vi content was 4.56 × 10-4 mol / g, methylphenyl silicone chain and 0.784 molar ratio of silicon atoms. Surface tension meter measured surface tension 32.312mN / m, measured with a UV spectrophotometer at 800nm light transmission rate of 98% or more.
2) the silicone oil and the obtained vinyl based polymer according to Si-H and Si-Vi mixing molar ratio of 1.5:1, adding 2ppm platinum catalyst, and follow the atomic molar ratio of inhibitor to platinum ratio of 1:1 Add methylbutynol, preparation a / B plastic, B gel crosslinking methylphenyl silicone oil mass of the total mass of B glue 0.1wt%.
3) the resulting A / B plastic were degassed under vacuum, at 80 ℃ curing 5h, obtain an LED package with silicone rubber.
Claims (6)
1 an easy vacuum deaeration of the LED package with the preparation of silicone rubbers, characterized in that
In by the following steps:
A) Preparation of transparent vinyl silicone oil: the N2Under the protection of the water removal under reduced pressure was added to the polymerizable monomer
Blocking agent, in the catalyst of the ring-opening polymerization; polymerization reaction is completed by heating points
Or the catalyst solution was removed by filtration, and removal of low molecular weight compound at high temperature under reduced pressure, cooled to room temperature,
Derived silica containing trifluoromethyl-propyl chain and methyl phenyl silicone chain transparent vinyl silicone oil;
2) in step 1) with a crosslinking agent obtained transparent vinyl silicone oil - methylphenyl silicone oil,
Platinum catalyst and inhibitor formulated into A / B plastic; A transparent vinyl silicone rubber, platinum catalyst and inhibition
Mixtures, according to the amount of platinum catalyst is a platinum atom silicone rubber mass, of the total mass of
2 ~ 50ppm, the amount of inhibitor in accordance with the molar ratio of inhibitor to platinum atoms is 1 ~ 100:1; B is methyl gum
Phenyl hydrogen silicone oil, methylphenyl silicone oil or vinyl silicone and a transparent mixture of methyl
Phenyl silicone oil were B dosage weight of the gum 0.01 ~ 99.99%; A / B transparent vinyl silicone gel
The total amount that, when A / B gel after mixing, to make one of the Si-H and Si-Vi molar ratio of 0.8 to 3:1;
The hydrogen-containing methylphenyl silicone oil content of 1.6wt% ~ 1.0 × 10
...-6wt％；
2) in step 1) with a crosslinking agent obtained transparent vinyl silicone oil - methylphenyl silicone oil,
Platinum catalyst and inhibitor formulated into A / B plastic; A transparent vinyl silicone rubber, platinum catalyst and inhibition
Mixtures, according to the amount of platinum catalyst is a platinum atom silicone rubber mass, of the total mass of
2 ~ 50ppm, the amount of inhibitor in accordance with the molar ratio of inhibitor to platinum atoms is 1 ~ 100:1; B is methyl gum
Phenyl hydrogen silicone oil, methylphenyl silicone oil or vinyl silicone and a transparent mixture of methyl
Phenyl silicone oil were B dosage weight of the gum 0.01 ~ 99.99%; A / B transparent vinyl silicone gel
The total amount that, when A / B gel after mixing, to make one of the Si-H and Si-Vi molar ratio of 0.8 to 3:1;
The hydrogen-containing methylphenyl silicone oil content of 1.6wt% ~ 1.0 × 10
...
Step 1), said polymerizable monomer consists of dimethyl siloxane ring, methyl vinyl siloxane ring,
Methyl phenyl rings and methyl trifluoropropyl siloxane cyclic siloxane composition; wherein dimethyl siloxane ring
The total amount of polymerizable monomer 10 ~ 50mol%, methyl vinyl siloxane ring of the total amount of polymerizable monomer
0.002 ~ 10mol%, trifluoropropyl methyl siloxane ring of the total amount of polymerizable monomer 0.05 ~ 12mol%; a
Phenyl ring siloxane as monomer hundred percent of the total moles of the other;
Dimethyl siloxane ring of the hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl
Cyclopenta siloxane in one or more, or a mixture of dimethyl siloxane ring; the methyl vinyl
Base ring Trimethyl vinyl siloxane cyclotrisiloxane, tetramethyl cyclotetrasiloxane vinyl five
Cyclopentasiloxane methyl vinyl siloxane five in one or more of; the methyl phenyl siloxane ring trimethyl
Triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, pentamethyl-cyclopenta siloxane pentaphenylbenzaldehyde
One or several, or a mixture of methyl phenyl ring body; the trifluoropropyl methyl siloxane ring A
Cyclotrisiloxane trifluoropropyl group, trifluoropropyl methyl cyclotetrasiloxane, cyclopentasiloxane trifluoropropyl methyl siloxane
In one or more alkyl;
...
Dimethyl siloxane ring of the hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl
Cyclopenta siloxane in one or more, or a mixture of dimethyl siloxane ring; the methyl vinyl
Base ring Trimethyl vinyl siloxane cyclotrisiloxane, tetramethyl cyclotetrasiloxane vinyl five
Cyclopentasiloxane methyl vinyl siloxane five in one or more of; the methyl phenyl siloxane ring trimethyl
Triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, pentamethyl-cyclopenta siloxane pentaphenylbenzaldehyde
One or several, or a mixture of methyl phenyl ring body; the trifluoropropyl methyl siloxane ring A
Cyclotrisiloxane trifluoropropyl group, trifluoropropyl methyl cyclotetrasiloxane, cyclopentasiloxane trifluoropropyl methyl siloxane
In one or more alkyl;
...
The catalyst of 98% concentrated sulfuric acid, CF3SO
3H, phosphoric acid, acid clay, strongly acidic cation
Ion exchange resins, rare earth solid superacid, tetramethyl ammonium hydroxide, tetramethyl ammonium hydroxide silicon alkoxides,
Tetraethyl ammonium hydroxide, tetraethyl ammonium hydroxide, silicon alkoxide, tetrabutyl ammonium hydroxide, tetra-n-butylammonium hydroxide
Ammonium, tetra-n-butylammonium hydroxide silicon alkoxide, hydroxide, tetrabutyl phosphonium hydroxide, tetrabutyl phosphine silicon alkoxide,
In one or more of KOH;
The platinum catalyst is chloroplatinic acid, H2PtCl
6The isopropanol solution, H2PtCl
6In tetrahydrofuran
Solution, Pt (PPh3)
4、Cp
2PtCl
2, Methyl vinyl siloxane complex of the platinum complex, phthalic
Diethyl platinum coordination complexes, platinum dichloride dicyclopentadiene, dichlorobis (triphenylphosphine) platinum complex
A;
The inhibitor of quinoline, pyridine, t-butyl hydroperoxide, propargyl alcohol, tetramethylammonium Alkynols
In one;
Step 1) The polymerization reaction temperature is 20 ~ 100 ℃, the polymerization reaction time is 1 ~ 20h; higher under reduced pressure
Removal of low molecular weight compounds in temperature-0.096MPa down gradually heated to 205 ℃ for;
Step 3) at room temperature vacuum deaeration time is 1 ~ 60min, curing temperature is 20 ~ 150 ℃.
(2) as claimed in claim 1, wherein the vacuum defoaming easy LED package made silicone rubber
Preparation method characterized in that in step 2), A / B vinyl silicone rubber in the total amount of the transparent, when the
A / B gel after mixing, Si-H and Si-Vi a molar ratio of 1 to 1.5:1.
3 according to claim 1 or 2, wherein the vacuum defoaming easy LED package with an organic silicone rubber
The preparation method is characterized in that said transparent vinyl silicone oil of the formula
ViMe2(MeViSiO)
m(MePhSiO)
p(Me
2SiO)
q(MeCH
2CH
2CF
3SiO)
kMe
2Vi, which, m,
p, q and K is 0 or a positive integer, 0 ≤ m ≤ 580,0 ≤ p ≤ 3308,0 ≤ q ≤ 3289,0 ≤ k ≤ 384,
And satisfy m / (m + p + q + k) = 0 ~ 0.1, p / (m + p + q + k) = 0.5 ~ 0.9, q / (m + p + q + k) = 0.1 ~ 0.5,
k / (m + p + q + k) = 0 ~ 0.12; vinyl silicone oil molecular weight of 500 ~ 50 × 104。
As claimed in claim 1 or 2, wherein the vacuum defoaming easy LED package with an organic silicone rubber
The preparation method is characterized in that step 1) the polymerizable monomer is removed under reduced pressure water temperature 35 ~ 45 ℃ / Pressure
Is 0.096Mpa; polymerization temperature is 80 ~ 100 ℃, the polymerization time is 1 ~ 5h; low score removed under reduced pressure
Compounds in-0.096MPa child under gradual warming to 205 ℃; Step 3) at room temperature vacuum deaeration time
5 ~ 40min, the curing temperature is 80 ~ 120 ℃.
5 according to Claim 1 or 2, wherein the vacuum defoaming easy LED package with an organic silicone rubber
The preparation method is characterized in that the platinum catalyst is H2PtCl
6The isopropanol solution, H2PtCl
6In tetrahydrofuran, methyl vinyl siloxane complex in one of platinum, platinum atoms in an amount in accordance with the
Silicone rubber mass, of the total mass of 2 ~ 30ppm.
As claimed in claim 5, wherein the vacuum defoaming easy LED package made silicone rubber
Preparation method of a platinum catalyst characterized in that said silicone rubber material for the total mass of 2 ~ 10ppm.
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| US20080039608A1 (en) * | 2006-08-11 | 2008-02-14 | General Electric Company | Oxetane composition, associated method and article |
| CN101289538B (en) * | 2008-05-30 | 2011-02-16 | 杭州师范大学 | Method for preparing methyl and phenyl hydrogen-containing silicon oil for packaging LED |
| JP4632069B2 (en) * | 2008-06-02 | 2011-02-16 | 信越化学工業株式会社 | Curable fluoropolyether coating agent composition |
| CN101343365A (en) * | 2008-08-28 | 2009-01-14 | 杭州师范大学 | Preparation method for methyl phenyl vinyl polysiloxane for packaging LED |
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| CN105950104A (en) * | 2016-06-30 | 2016-09-21 | 杭州福斯特光伏材料股份有限公司 | High-temperature-resistant light emitting diode (LED) lamp filament encapsulation adhesive |
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